U.S. patent number 4,112,179 [Application Number 05/639,503] was granted by the patent office on 1978-09-05 for method of coating with ablative heat shield materials.
Invention is credited to Joseph W. Maccalous, Donald A. Thomas.
United States Patent |
4,112,179 |
Maccalous , et al. |
September 5, 1978 |
Method of coating with ablative heat shield materials
Abstract
A novel method for the spray application of an ablative material
to produce a coating having low density, high tensile strength and
improved char retension comprising spraying a composition of
silicone resin, silicaceous fibers and hollow silicaceous
microspheres in a solvent and curing to form an ablative coating
having a density of 10 to 15 lbs/ft.sup.3.
Inventors: |
Maccalous; Joseph W.
(Littleton, CO), Thomas; Donald A. (Englewood, CO) |
Family
ID: |
24564367 |
Appl.
No.: |
05/639,503 |
Filed: |
December 10, 1975 |
Current U.S.
Class: |
428/325; 427/387;
427/388.2; 427/407.1; 427/409; 427/427.4; 428/447; 428/450;
428/920; 521/54; 523/218; 524/16; 524/789; 525/474 |
Current CPC
Class: |
B05D
5/02 (20130101); C08J 9/32 (20130101); C09D
5/00 (20130101); C09D 183/04 (20130101); C09D
183/04 (20130101); C08K 5/0016 (20130101); C08K
7/10 (20130101); C08K 7/16 (20130101); C08K
5/0016 (20130101); C08L 83/04 (20130101); C08K
7/16 (20130101); C08L 83/04 (20130101); B05D
7/54 (20130101); B05D 7/58 (20130101); C08J
2383/04 (20130101); C08L 2666/54 (20130101); Y10T
428/31663 (20150401); Y10T 428/252 (20150115); Y10S
428/92 (20130101) |
Current International
Class: |
B05D
5/00 (20060101); C08J 9/32 (20060101); C08J
9/00 (20060101); C09D 5/00 (20060101); C09D
183/04 (20060101); B32B 005/16 (); B05D
001/02 () |
Field of
Search: |
;427/154,156,421,427,409,387,388A,47R ;428/447,450,920,325
;260/33.6SB,37SB,826 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gwinnell; Harry J.
Attorney, Agent or Firm: Sughrue, Rothwell, Mion, Zinn and
Macpeak
Claims
What is claimed is:
1. A method for producing an ablative coating on a surface
consisting essentially of:
preparing a sprayable coating composition by mixing components
consisting essentially of the following ingredients
(a) a silicone resin;
(b) a solvent system comprising 85-100% n-heptane and 15-0% of a
higher boiling inert solvent;
(c) silicaceous fibers; and
(d) hollow microspheres of silicaceous material, and
subsequently and in a separate step spraying the sprayable coating
composition on said surface, followed by curing the thus-formed
coating to form an ablative coating having a density of about 10 to
15 lbs/ft.sup.3.
2. The method of claim 1, including the step of applying a coating
of a silicone primer to said surface prior to spraying said
sprayable coating composition.
3. The method of claim 2, including the step of applying an
adhesive to the said coating of primer prior to spraying said
sprayable coating composition.
4. The method of claim 1, wherein said curing is at room
temperature.
5. The method of claim 1, wherein filler material is added to the
sprayable coating composition before the spraying step.
6. The method of claim 1, wherein said higher boiling solvent is
xylene.
7. The method of claim 1, wherein said solvent system is a mixture
of about 96% n-heptane and about 4% xylene.
8. The method of claim 5, wherein said filler material is at least
one of ground cork, phenolformaldehyde microspheres, carbon powder
and powdered silica.
9. The method of claim 8, wherein the sprayable coating composition
consists essentially of:
(a) 2114.7 parts by weight of silicone resin;
(b) 7500.0 parts by weight of solvent comprising:
(i) 7200 parts by weight of n-heptane; and
(ii) 300 parts by weight of xylene
(c) 600 parts by weight of glass fibers about 1/4 inch in length
and about 0.0004 inch in diameter;
(d) 1385.0 parts by weight of hollow microspheres of silicaceous
material; and
(e) 1438.8 parts by weight of fillers comprising:
(i) 1155.0 parts by weight of ground cork;
(ii) 230.0 parts by weight of phenolformaldehyde microspheres;
and
(iii) 53.8 parts by weight of powdered carbon.
10. The method of claim 1, wherein said silicone resin component
(a) is a two-part resin system, one part of which comprises a
curing agent for the second part.
11. The product produced by the process of claim 1.
Description
BACKGROUND OF THE INVENTION
A. Field of Invention
The present application relates to a novel coating system which can
be used on specific areas of ascent and re-entry vehicles or in any
other application in which ablative coatings may be
advantageous.
B. Description of Prior Art
Heretofore in the art of forming ablative heat shield coatings, one
method utilized expensive pressure molds or dies into which batches
of materials were placed and vacuum cured at 300.degree. F. The
resultant molded coating was then machined and applied by secondary
bonding under a pressure of 1-3 psi to the specific surface for
which the mold was intended. This process involves clear and
numerous disadvantages, such as the use of expensive molds and
dies, high labor costs and the necessity of mixing large batches of
materials.
Additionally, U.S. Pat. No. 3,553,002 - Haraway, Jr., et al.,
teaches a sprayable ablative system which has the distinct
disadvantage of producing a coating with a relatively high density
of over 35 lbs/ft.sup.3.
The prior art method described in U.S. Pat. No. 3,210,233, Kummer
et al., involves a non-metallic honeycomb having a heat insulating
and ablative composition in the cells. This arrangement has the
disadvantages of difficulty in applying the ablative and in the
expense of the honeycomb.
It is an object of this invention, therefore, to provide a method
for producing sprayable ablative compositions capable of depositing
ablative coatings having lower density than the prior art products
and at the same time having increased thermal improved properties
of insulation and adherence.
In addition, it is an object of this invention to produce a method
of applying such ablative coatings simply, inexpensively and in a
manner that allows close control of the coating thickness.
SUMMARY OF THE INVENTION
The present invention comprises a composition comprising the
following constituents:
1. A flexible silicone resin component, such as, RTV-652, RTV-655,
Silgard-182, etc.
2. A silicaceous component including, for example, 1/4 inch fibers
of glass and silica, 1/2 inch fibers of glass and silica, and 1
inch fibers of glass.
3. A hollow microsphere component including microspheres of carbon,
glass and silica.
4. A solvent component to dissolve the resin and serve as carrier
for the other components, comprising n-heptane.
5. As an optional component, a filler such as carbon, cork, silica,
polymer spheres, etc.
In this invention the selection of n-heptane as a solvent allows
for the laying down of a uniform sprayed layer of heat shield
material. By varying the spraying technique, ablators with
densities ranging from 10 to 15 lbs/ft.sup.3 can be produced. This
reduced density is apparently due in part to a distribution of fine
voids which are left when the solvents evaporate. This marked
advance in the reduction of ablative heat shield coating density
vastly improves the desired characteristics by lowering thermal
conductivity, reducing the ablator weight and possibly increasing
flexibility and elongation. Use of this invention on ascent and
re-entry vehicles will prove of great value since minimum ablator
weight is critical in these applications.
It has been found that the solvent utilized in the spray
application of an ablator system is critical to the characteristics
of the final product. Specifically, it has been found that if the
solvent utilized does not evaporate quickly enough, subsequently
sprayed layers of the ablator will "trap" the solvent in the lower
layers and cause higher ablator density. Additionally, the
"trapped" solvent might contain impurities that, if allowed, to
stay beneath the surface, will interfere with the curing mechanism
of the resin system.
If the solvent chosen evaporates or "flashes" too quickly, a
gradient will occur whereby the outer surface of each of the
sprayed layers will be substantially drier than the interior of
that layer. Subsequent spraying will result in the new "wet" layer
coming into contact with a substantially drier layer, to produce a
bond between the layers that is weaker than desired. Thus,
inter-layer peeling may result.
It has been found that the use of an n-heptane based solvent system
results in an ablative coating of low density, high strength and
increased flexibility. Further, n-heptane is useful for a wide
variety of resin systems. Modifications to this basic solvent can
be made to achieve optimum ablator and spraying
characteristics.
In accordance with the present invention, a novel method for the
application of an ablative coating is provided together with the
resultant improved ablative coatings by which an improved ablative
protection for various purposes is obtained.
DETAILED DESCRIPTION OF THE INVENTION
Each of the components of the sprayable ablative coating
composition of this invention is discussed in detail below.
1. Flexible Silicone Resin Component
Resins for use in this invention can be the room temperature
vulcanizing (RTV) silicone rubbers which are well-known in the art.
Among the RTV silicone resins the two-part, fast curing materials
are RTV-652 and RTV-655 resins maufactured by General Electric
Company.
Alternatively, silicone resins which require a higher curing
temperature may be utilized. Preferred among these resins is the
SYLGARD resin system manufactured by Dow Corning.
The General Electric RTV-652 resin is produced by mixing the "A"
and "B" portions. The "A" portion is a dimethyl polysiloxane
containing phenyl groups for low temperature properties, vinyl
groups for reactivity and a soluble platinum catalyst in the 1-50
ppm range. The "A" portion has a viscosity of 4,000 centipoise at
77.degree. F. and a refractive index of 1.43. The "B" portion is a
dimethyl polysiloxane containing silicone hydride groups which,
upon mixing with the "A" portion, add across the unsaturated double
bond of the vinyl group. The resin is cured by mixing one part of
the "B" portion to 10 parts of the "A" portion. This material has a
pot life of 7 to 12 minutes.
The SYLGARD-182 silicone resin cures as moderate temperatures,
e.g., 65.degree. C., for 4 hours, but can be accelerated by using
higher temperatures. This is also a two-part resin wherein one part
of curing agent is with the ten parts of the base resin.
Alternately, two resin systems such as RTV-652 and RTV-655 may be
used together to achieve the desired properties.
2. Silicaceous Fiber Component
The preferred fiber systems for use in this invention are fibrous
silicaceous materials of lengths up to about 1 inch. The optimum
fiber length is about 1/4 inch, although longer fibers may be
utilized, but this tends to lead to difficulty in spraying and to
relatively non-uniform spraying.
Especially preferred for use as the fibrous component is "Refrasil"
manufactured by E. I. DuPont Company. The optimum available size
for the purpose of this invention is "Refrasil" F100-A25, a 1/4
inch in length and approximately 0.0004 inch in diameter and has a
bulk density of about 13 lbs/ft.sup.3. A typical composition of the
"Refrasil" is as follows:
______________________________________ % %
______________________________________ SiO.sub.2 99.3 CaO 0.01
TiO.sub.2 0.38 MgO 0.01 Al.sub.2 O.sub.3 0.18 Na.sub.2 O 0.002
ZrO.sub.2 0.02 K.sub.2 O 0.005 B.sub.2 O.sub.3 0.07 Li.sub.2 O
0.0002 ______________________________________
Glass fibers can be utilized alone or mixed with silica fibers.
3. The Hollow Microsphere Component
The small hollow spheres for use in this invention may be composed
of materials such as carbon, glass or silica.
Preferred among these materials are the "SI Eccospheres"
manufactured by Emerson & Coming, Inc., of Caton,
Massachusetts. This material is composed of silicon and has a bulk
density of about 11 lbs/ft.sup.3 particle size of 30-125 microns
with a wall thickness of about 2 microns.
Alternatively, materials such as "IG-101 Eccospheres" and "R
Eccospheres", also may be utilized if lower cost is desired. The
"IG-101" hollow spheres manufactured by Emerson & Cuming, Inc.,
are composed of sodium borosilicate, glass and have a bulk density
of about 15 lbs/ft.sup.3 particle size of 10-250 microns with a
wall thickness of about 2 microns.
The "R" hollow spheres are composed of electrical grade glass and
have a bulk density of about 14 lbs/ft.sup.3, particle size of
30-200 microns with a wall thickness of about 2 microns.
Apparently no change in basic physical properties results from the
substitution of "R" or "IG-101 Eccospheres" for the "SI" material
except that the use of "IG-101" spheres increases the density of
the final material by about 2 lbs/ft.sup.3.
The thermal conductivity of these materials is about 0.45
BTU/hr/.degree. F./sq.ft/in for IG-101 and R, with a value of about
0.40 BTU/hr/.degree. F./sq.ft/in for the SI material.
4. Filler Component
Materials such as cork, "Phenolic Microballoons", carbon spheres,
carbon and CAB-O-SIL may be added to the ablative of this invention
to effect certain properties.
Cork may be employed to reduce density and improve the insulative
properties. Especially useful is the material designated "Prime
Milled Ground Cork" with a sieve size of 20/40 and a bulk density
of 6-8 lbs/ft.sup.3.
"Phenolic Microballoons", a registered trademark of Emerson Cuming,
Inc., of Canton, Massachusetts, are small hollow spheres of
phenolformaldehyde resin and can be used to lower thermal
conductivity and improve char formation. Especially preferred are
BAKELITE Phenolic Microballoons, available from Union Carbide
Corporation under the designation BJO-0930, which have a maximum
bulk density of 6.5 lbs/ft.sup.3 and a maximum liquid displacement
density of 0.21-0.25 g/cc. This material has a size range of 0.0002
to 0.005 inch in diameter with an average particle size of about
0.0017 inch in diameter.
Carbon powder provides a high emissive element which helps provide
reradiative properties in the product as well as improved spraying
characteristics in the application as seen by a reduction in spray
pressures. Additionally, tensile properties improved from 10-15 psi
to 25-30 psi with no increase in density of the final product.
Especially preferred is carbon designated as P-33, available from
R. T. Vanderbilt Corporation, which is a 99.5% pure amorphous
carbon powder with an average particle size of 320 millmicrons and
a bulk density of 1.91 lbs/ft.sup.3.
CAB-O-SIL, made by the Cabot Corporation of Boston, Massachusetts,
is a submicroscopic fire-dry silica which can have an average
diameter of from 70 to 500 angstroms and a surface area of from
-100 m.sup.2 /g to 50 m.sup.2 /g., depending on the grade
selected.
All fillers should be free from contaminants such as sulphur which
may interfere with the resin curing. This can be effected by
washing with a suitable solvent such as methyl ethyl ketone and
vacuum drying to remove all solvent.
Other fillers which can be used within the scope of this invention
are graphite fibers, wood shavings, alumina fibers and similar
materials.
The solid fillers and fibers used may be coated with a silane
coupling agent before their addition to the resin.
5. The Solvent Component
As solvents and carriers for the ablative compositions of this
invention, systems based on n-heptane have been found to be
suitable. Freon, or similar solvents, may be used but they are more
expensive and give a somewhat weaker and more porous coating.
The preferred solvent system is a combination of n-heptane and a
higher boiling inert solvent, for example, xylene. The higher
boiling solvent is employed to extend the "flash" time of the
sprayed composition as desired to permit optimum interlayer
knitting. This is believed to be accomplished by a mechanism
whereby the sprayed composition remains semi-liquid, due to the
lower evaporation rate of the higher boiling liquid, long enough to
allow the more deeply deposited solvents to surface and
evaporate.
Especially preferred is a solvent system comprising 85 to 100%
n-heptane and 15 to 0% xylene.
Various ablative compositions were made to demonstrate the improved
properties which can be obtained by employing this invention.
EXAMPLE 1
Especially preferred among the ablative compositions within the
scope of this invention is the composition set forth below which
contains a mixture of the RTV-652 and RTV-655 resins described
above, has a pot life of 45-60 minutes and cures at room
temperature within 24 hours.
______________________________________ COMPONENT gm %
______________________________________ 1. Resin RTV-652 A 1000.0
18.06 B 100.0 1.80 RTV-655 A 922.5 16.66 B 92.2 1.66 2. Fibers
F-100-A25 Refrasil 600.0 10.83 3. Microspheres SI Eccospheres
1385.0 25.02 4. Filler Cork 1155.0 20.85 Phenolic Microballoons
230.0 4.15 P-33 Carbon 53.8 0.97 5538.5 gms 100.00% 5. Solvent
n-heptane 7200.0 96.00 xylene 300.0 4.00 7500.0 gms 100.00%
______________________________________
The cork SI Eccospheres and microballoons of the above compositions
are preferably pretreated to remove any contaminants and
hydrocarbons according to the following schedule:
Cork
1. Wash in water (2.5 gal per 500 gms. of cork) and drain;
2. Wash in methyl ethyl ketone (2.5 gal. per 500 gms. of cork),
drain and dry;
3. Add a silane coupling agent and cure at room temperature;
and
4. Screen through 100 mesh screen to break up large lumps.
SI Eccospheres and Phenolic Microballoons
1. Wash both in methyl ethyl ketone (2.5 gal. per 1000 gms.
material), drain and dry;
2. Screen materials through a 100 mesh screen to break up large
lumps.
After this pretreatment, the components are weighed out and
assembled according to the following schedule:
1. The "A" portions of two resins are blended for 1-2 minutes;
2. The F100-A25 fibers are added and the blending continued for 3-4
minutes;
3. The product from Step (2) above is milled through a three-roll
paint mill 3 or 4 times;
4. The milled product from Step (3) is then placed in a mixer and
mixed for 5-6 minutes with the SI Eccospheres, cork, phenolic
microballoons and carbon to yield the "A" portion of the
composition; and
5. The "B" portions of the resins are blended for 1-2 minutes to
yield the "B" catalyst portions of the composition.
If the composition is formulated with only the RTV-655 resin, a 24
hour cure at 300.degree. F. is required.
EXAMPLE 2
A composition was prepared in a similar manner to that of Example 1
except that a higher curing temperature silicone resin (SYLGARD
182) and catalyst is substituted for the RTV-652 and -655 resin
component, and only SI Eccospheres and F100-A25 fibers were used
according to the following formulation:
______________________________________ SYLGARD 182A & B 29.7%
SI Eccospheres 61.9% F100-A25 Fibers 8.4% 100.0%
______________________________________
Xylene and n-heptane were used in the proportions shown in Example
1. The resulting composition has the advantage of being basically
an all silica system and is therefore RF transparent. Density is
increased to 15 lbs/ft.sup.3, but a sample of this material has
been cycled to 1200.degree. to 1600.degree. F., over 100 times with
a weight loss of only 6%, the weight stabilizing after 10-20
cycles.
The following spray procedure exemplifies the preferred mode of
operation in accordance with the invention.
A plate composed of an aluminum alloy is first thoroughly cleaned
with a cloth moistened with methyl ethyl ketone or other suitable
solvent to render the plate free of grease, oil, fingerprints, etc.
A primer such as silicone primer, especially Dow Corning 1200, is
then applied to the clean plate to form an even application of two
cross coats. Each coat is cured for at least 1 to 4 hours depending
on humidity, the lower the humidity the more time is required, at
room temperature, whereby each coat produces a dry film having a
thickness of 0.00005 to 0.0002 inch. The primer should extend
beyond the edge of the final coating by about 1/4 inch.
A base adhesive coat is applied to the primed plate. The base
adhesive can preferably be a modification of the resin composition
utilized. That is, for Example 1 a suitable base coat can be made
from RTV-652, RTV-655, Cab-O-Sil and carbon powder with the
n-heptane:xylene solvent system.
The base adhesive coating is sprayed onto the primed plate to
produce an even, wet layer weighing 0.005 to 0.01 lbs/ft.sup.2 with
a density of about 60 lbs/ft.sup.3.
As soon as possible, the primed, wet adhesive-coated plate is
sprayed with the ablative compound of this invention, for instance
the composition of Example 1, preferably in separate coats each
about 0.03 to 0.04 inch in thickness. Each coat should preferably
be applied within 2 to 5 minutes of the previous one.
The coated product is then cured. When using the composition of
Example 1, the coated product can be cured according to the
following schedule:
1. For about 24 hours at 70.degree. to 100.degree. F.; or
2. For about 8 hours at 70.degree.-100.degree. F. followed by about
a 2 hour cure in a vented air oven at about 150.degree. F.
The ablative composition of this invention may also be used as a
peelable layer for use at locations other than the surface that had
been sprayed. This may be accomplished by directly spraying the
ablative composition onto a suitable surface such as metal or
teflon without first priming or spraying adhesive thereon. After
curing, the produced ablative layer may be peeled from the surface
and utilized elsewhere, e.g., applied by secondary bonding to
another surface.
The cured product has a velvety texture, is uniformly coated and
free from blisters, nodules, delamination, contamination and voids
greater than 1/32 inch in diameter. Preferably, the product will
have a Shore "A" hardness of at least about 30.
* * * * *